Silver halide color photographic material containing yellow coupler

ABSTRACT

Color photographic material is provided which contains at least one silver halide emulsion layer containing a yellow color coupler of the formula ##STR1## wherein G is the radical of a yellow coupler which is bonded to the heterocyclic ring by means of the active methylene group, Z is --CO-- or --SO 2  --, M is hydrogen if Z is --CO--; or a substituent and R is hydrogen or a substituent.

The new two-equivalent yellow couplers lead due to their improvedreactivity (high maximum density), minimal fog and high fastness tolight and outstanding spectral properties of the dyestuffs formedtherefrom to a colour photographic material of advantageous properties.

In order to produce coloured photographic images, exposed silver halideemulsion layers which at the same time contain colour couplers are, asis known, developed with a developing agent which contains aromaticprimary amino groups. The oxidised developing agent then reacts with thecolour coupler with the formation of an image dyestuff, the amount ofthis dyestuff being dependent on the amount of incident light.

In general, a light-sensitive photographic multi-layer material whichconsists of a red-sensitive layer, which contains the cyan coupler, agreen-sensitive layer, which contains the magenta coupler, and ablue-sensitive layer, which, in turn, contains the yellow coupler, isused. On colour development, the corresponding dyestuffs which are cyan,magenta and yellow in colour, are formed.

Usually, phenols or α-naphthols are employed as cyan couplers,pyrazolones are employed as magenta couplers and acylacetylamides areemployed as yellow couplers. The dyestuffs formed after development arethen indophenols, indamines or azomethines.

Conventional colour couplers possess an active methylene group and fourequivalents of silver halide are required in order to convert these intothe corresponding image dyestuff; therefore colour couplers of this typeare called four-equivalent couplers. Colour couplers in which onehydrogen atom of the active methylene group is replaced by a group whichcan be split off during the coupling reaction are also known. In thiscase two equivalents of silver halide are required in order to producethe corresponding image dyestuff. Therefore, colour couplers of thistype are termed two-equivalent couplers.

Compared with the four-equivalent couplers, two-equivalent couplers aredistinguished by the advantages which follow:

1. The amount of silver halide required for the formation of the sameamount of dyestuff is only half as great; there is thus a noticeablereduction in the manufacturing costs for a photographic material;

2. The light-sensitive layer can be kept thinner, by which means thesharpness and the resolution of the resulting colour image are improved;and

3. The sensitivity of the lower layers is increased as a result of theincreased light transmittance, since the thickness of the upper layersis reduced.

In the case of the yellow couplers, essentially the following leavinggroups have been proposed, to date, for two-equivalent couplers:

halogen atoms, such as are described, for example, in GermanOffenlegungsschrift 2,114,577, French Patent Specifications Nos. 991,453and 869,169 or U.S. Pat. Nos. 2,728,658 and 3,277,155;

the group --OR, in which R represents alkyl, aryl, a heterocyclicradical or acyl, such as are described, for example, in British PatentSpecification No. 1,092,506, French Patent Specifications Nos. 1,411,385and 1,385,696 or in U.S. Pat. Nos. 3,447,928 and 3,408,194;

the --SR" group which is described in British Patent Specification No.953,454 or U.S. Pat. No. 3,265,506;

the 1,2,3-benztriazolyl group of the formula ##STR2## (GermanOffenlegungsschrift 1,800,420) the radicals --SO₃ H and --SCN (BritishPatent Specification No. 638,039 and U.S. Pat. No. 3,253,924)

imide groups of the formulae ##STR3## (German Offenlegungsschriften2,163,812, 2,313,461, 2,057,941, 2,261,361, 2,431,480 and 2,219,917);radicals of the formula ##STR4## (German Offenlegungsschrift 2,329,587);leaving groups of the formula ##STR5## (German Offenlegungsschrift2,433,812) leaving groups of the formula ##STR6## wherein V, togetherwith --C═C--grouping, forms an aromatic ring of the benzene series or aheterocyclic ring with at least one nitrogen atom (GermanOffenlegungsschrift No. 2,414,006), leaving groups of the formula##STR7## according to German Offenlegungsschrift No. 2,528,638 or insome cases according to German Offenlegungsschrift No. 2,442,703,leaving groups of the formula ##STR8## according to GermanOffenlegungsschrift No. 2,442,703 and certain pyridones and pyridazonesaccording to German Offenlegungsschrift No. 2,318,807.

The object of the present invention is to provide readily accessibletwo-equivalent couplers, for materials for colour photography, which,compared with known two-equivalent couplers, are distinguished byimproved reactivity (high maximum density), minimal fog, high fastnessto light and outstanding spectral properties of the dyestuffs formedtherefrom.

The subject of the invention is a material, for colour photography,which contains at least one silver halide emulsion layer which contains,as the yellow coupler, a compound of the formula ##STR9## in which G isa radical of a yellow coupler, which is bonded to the heterocyclic ringby means of the active methylene group, Z is --CO-- or --SO₂ --, M ishydrogen, if Z is --CO--, or a substituent, for example alkyl with 1 to18 carbon atoms, optionally substituted by halogen, hydroxyl, nitro,cyano, alkoxy, aryloxy or amino, aralkyl, cycloalkyl with 1 to 4cycloalkyl rings, phenyl, optionally substituted by lower alkyl or loweralkoxy, halogen, acylamino, sulphonic acid groups, sulphonic acid amidegroups, carboxylic acid groups, carboxylic acid amide groups, carboxylicacid ester groups, hydroxyl, nitro, cyano, amino, mercapto,alkylmercapto or --SO₂ W or --COW, in which W is alkyl with 1 to 18carbon atoms, optionally substituted by halogen, nitro, cyano, amino oralkoxy with 1 to 18 carbon atoms, cycloalkyl, aryl, pyridyl, pyrimidyl,furyl or thienyl, M is also pyridyl, furyl, thienyl or perfluoroalkyl,acyl or dialkylamino, with, in each case, up to 5 carbon atoms in thealkyl part, alkoxy with 1 to 18 carbon atoms or phenoxy and R ishydrogen or a substituent, such as, for example, alkyl with 1 to 18carbon atoms, aralkyl, aryl, pyridyl, pyrimidyl, furyl, thienyl,cycloalkyl, alkoxy with 1 to 18 carbon atoms, aryloxy, alkylmercaptowith 1 to 18 carbon atoms, arylmercapto, halogen, acyl, acyloxyalkyl,trifluoromethyl, cyano, a primary amino group, a mono- or di-alkylaminogroup, in which the alkyl radicals each contain 1 to 18 carbon atoms, orone of the groups M--Z--HN--, W--CO--, ##STR10## W--SO₂ --, --SO₂ NH₂,##STR11## W--CO--O-- or W--O--CO--, in which E is alkyl with 1 to 5carbon atoms, E' is hydrogen or alkyl with 1 to 5 carbon atoms and M, Wand Z have the indicated meanings.

The invention also relates to a process for the production of a yellowimage, wherein a material, for colour photography, which contains, on asupport, at least one silver halide emulsion layer containing, as theyellow coupler, at least one compound of the formula (1), is exposed andthe exposed material is treated with an aqueous alkaline solution whichcontains an aromatic amine as the developer.

The invention also relates to the yellow images produced by thisprocess.

The invention furthermore relates to the new yellow couplers of theformula (1).

The radicals G, of a yellow coupler, in compounds of the formula (1)are, as a rule, open-chain radicals, containing methylene groups, ofyellow couplers, especially benzoylacetanilide or pivaloylacetanilideradicals, the latter being preferred.

The radical M in the compounds of the formula (1) can be hydrogen onlywhen Z is --CO--. M is also alkyl with 1 to 18 carbon atoms and thesealkyl radicals can be straight-chain or branched, such as, for example,methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert.-butyl,amyl, n-hexyl and n-heptyl; and octyl, nonyl, decyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, includingthe various isomers in each case.

These alkyl radicals can be substituted by halogen atoms, especiallyfluorine, chlorine, (--CH₂ Cl, --CCl₃) or bromine; hydroxyl, nitro orcyano; alkoxy, especially with 1 to 5 carbon atoms in the alkoxy part,such as, for example, --CH₂ --O--C_(n) H_(2n+1), in which n is 1 to 5;aryloxy, especially ##STR12## amino, such as, for example, NH₂,--NHC_(n) H_(2n+1) or --N(C_(n) H_(2n+1))₂, in which n is 1 to 5. M isalso cycloalkyl, such as cycloalkyl with 1 to 4 cycloalkyl rings and 5to 10 carbon atoms, for example pentyl, hexyl, norbornyl or 1-adamantyl;aralkyl, especially benzyl; phenyl, optionally substituted by --C_(n)H_(2n+1) or --O--C_(n) H_(2n+1), in which n is 1 to 5, for example,methyl, ethyl, propyl, butyl, amyl and isomeric radicals or methoxy,ethoxy, propoxy, butoxy, pentoxy and isomeric radicals, halogen,especially chlorine and bromine, or acylamino, especially --NHCOC_(n)H_(2n+1) and ##STR13## in which n is 1 to 5; SO₃ H, sulphonic acid amidegroups, such as --SO₂ NH₂, --SO₂ N(C_(n) H_(2n+1))₂ and --SO₂ NH(C_(n)H_(2n+1)), --COOH, carboxylic acid amide groups, such as --CONH₂,--CON(C_(n) H_(2n+1))₂ and --CONH(C_(n) H_(2n+1)), carboxylic acid estergroups, such as --COOC_(n) H_(2n+1), ##STR14## and ##STR15## hydroxyl,nitro, cyano, amino groups, such as --NH₂, --NHC_(n) H_(2n+1) or--N(C_(n) H_(2n+1))₂, mercapto (--SH) or alkylmercapto, especially ofthe formula --SC_(n) H_(2n+1). Further substituents on the phenylnucleus can correspond to the formula --SO₂ W or --COW, in which W canbe alkyl with 1 to 18 carbon atoms (as indicated above). The alkylradicals W can be substituted by halogen, for example chlorine orbromine, nitro, cyano, amino or alkoxy with 1 to 18 carbon atoms.Cycloalkyl, especially cyclohexyl, aryl, especially phenyl, which isoptionally also substituted, pyridyl, pyrimidyl, furyl or thienyl arefurther meanings of W. The radical M can also be pyridyl, furyl orthienyl perfluoroalkyl, especially a radical of the formula C_(n)F_(2n+1), acyl, such as, for example, benzoyl, dialkylamino, especiallyof the formula --N(C_(n) H_(2n+1))₂, alkoxy with 1 to 18 carbon atoms(--OC_(m) H_(2m+1), m = 1 to 18) or phenoxy ##STR16## the index n alwayshas the meaning 1 to 5.

The radical R in the compounds of the formula (1) is hydrogen, alkylwith 1 to 18 carbon atoms (as indicated above), aralkyl, especiallybenzyl, or aryl, especially phenyl and also phenyl substituted byhalogen (Cl or Br), --CN, --NO₂, --OH, --O--C_(m) H_(2m+1), --C_(m)H_(2m+1), --NH₂, ##STR17## --NH--OC--W₁, --NH--SO₂ --W₁, --CO--W₁, --SO₂--W₁, --S--C_(m) H_(2m+1), sulphonic acid amide (including those havingsubstituents on the nitrogen atom), carboxylic acid amide (includingthose having substituents on the nitrogen atom), --COOH or --COOW₁.

W₁ can have the following meanings: --C_(m) H_(2m+1) (m = 1 to 18),cyclohexyl, adamantyl, phenyl which is optionally further substituted by--C_(m) H_(2m+1), --O--C_(m) H_(2m+1), --Cl, --Br, --CN, --OH,--NH--OC--C_(n) H_(2n+1), ##STR18## --S--C_(m) H_(2m+1), --SO₂ --C_(n)H_(2n+1), ##STR19## sulphonic acid amide (including those havingsubstituents on the nitrogen atom), carboxylic acid amide (includingthose having substituents on the nitrogen atom), --COOH, --CO--O--C_(n)H_(2n+1), ##STR20## pyridyl, furyl or thienyl.

The radical R is also pyridyl, pyrimidyl, furyl, thienyl, cycloalkyl,especially with 1 to 4 cycloalkyl rings and 6 to 10 carbon atoms, suchas, for example, cyclohexyl, norbornyl or 1-adamantyl, alkoxy with 1 to18 carbon atoms (alkoxy radicals analogous to the alkyl radicalsmentioned), alkoxy with 1 to 5 carbon atoms, such as methoxy, ethoxy, n-and iso-propoxy, n-butoxy and n-pentoxy, being preferred, or aryloxy,especially phenoxy, alkylmercapto with 1 to 18, and especially 1 to 8,carbon atoms, such as, for example, methylmercapto, ethylmercapto,n-propylmercapto, iso-propylmercapto, butylmercapto, pentylmercapto,hexylmercapto, heptylmercapto and octylmercapto, arylmercapto,especially phenylmercapto, halogen, especially chlorine and bromine,acyl, especially benzoyl, acyloxyalkyl, especially benzoyloxyalkyl with1 to 5 carbon atoms in the alkyl part, for example ##STR21##trifluoromethyl, cyano, an amino group, especially --NH₂ or ##STR22## ora mono- or di-alkylamino group with 1 to 18 carbon atoms in the alkylpart, especially of the formulae --NHC_(n) H_(2n+1) and N(C_(n)H_(2n+1))₂, in which n is 1 to 5; in addition, R can also denote theradicals M--Z--NH--, W--CO--, especially W₁ CO--, ##STR23## especially##STR24## W--SO₂ --, especially W₁ SO₂, --SO₂ NH₂, ##STR25## W--COO--,especially W₁ --COO--, and WOCO--, especially W₁ OCO--. M, W, W₁ and Zhave the indicated meanings, E is alkyl with 1 to 5 carbon atoms and E'is hydrogen or alkyl with 1 to 5 carbon atoms.

The data regarding further substitution are to be understood to meanthat the particular radicals can contain one or more than one of theindicated substituents. The dialkylamino groups of the formula ##STR26##can also contain two different alkyl groups on the same nitrogen atom.

The substituent G in the compounds of the formula (1) is a radical,especially an open-chain radical, of a yellow coupler which is bonded bymeans of the active methylene group, that is to say the carbon atombonded to the thiadiazolyl ring is not a constituent of a ring.Preferably, the substituent G is an acylacetic acid amide radical whichis bonded to the thiadiazolyl ring by means of the α-carbon atom of theacetic acid group, acyl (Q--CO--) being, in particular, pivaloyl andoptionally substituted benzoyl and amide being, in particular, anilidewhich is optionally substituted on the phenyl ring.

Further possible acyl radicals (Q--CO--) are those in which Q is alkylwith at most 32 carbon atoms, α-alkoxyalkyl with 2 to 32 carbon atoms,α-aryloxyalkyl with 7 to 40 carbon atoms, cycloalkyl with 1 to 4alicyclic rings, or an aryl (preferably benzene) or heterocyclic radicalwhich is optionally further substituted by alkyl or alkoxy with 1 to 18carbon atoms, halogen, such as chlorine or bromine, acylamino(especially derived from carboxylic acids), sulphonic acid amide orcarboxylic acid amide.

The aryl or heterocyclic radical can be substituted by one or moresubstituents.

Preferred radicals Q are tertiary butyl, norbornyl,[2,2,2]-bicyclooctyl, phenyl, 3,4-methylenedioxyphenyl orp-methoxyphenyl.

The phenyl ring of the anilide can be substituted by one or more of thefollowing substituents: halogen, such as chlorine or bromine, alkyl andalkoxy, especially with 1 to 5 carbon atoms, acylamino, preferablyderived from carboxylic acids, sulphonic acid amide, carboxylic acidamide or carboxylic acid esters, especially carboxylic acid alkylesters.

The acylamino or carbox(sulphon)amido groups can also carry the ballastgroups which are customary for colour couplers and are in themselvesknown.

The materials, according to the invention, for colour photographycontain, as yellow couplers, in particular compounds of the formula (1),in which G is a radical of a yellow coupler which is bonded to theheterocyclic ring by means of the active methylene group, Z is --CO-- or--SO₂ --, M is hydrogen, if Z is --CO--, or alkyl with 1 to 18 carbonatoms, optionally substituted by halogen, nitro, cyano, alkoxy or amino,aralkyl, cycloalkyl, phenyl, optionally substituted by alkyl, alkoxy,halogen, acylamino, sulphonic acid groups, sulphonic acid amide groups,carboxylic acid groups, carboxylic acid amide groups, carboxylic acidester groups, hydroxyl, nitro, cyano, amino, mercapto, alkylmercapto or--SO₂ --W or --CO--W, in which W is alkyl with 1 to 18 carbon atoms,optionally substituted by halogen, nitro, amino or alkoxy with 1 to 18carbon atoms; or W is cycloalkyl, aryl, pyridyl, pyrimidyl, furyl orthienyl; M is also pyridyl, furyl, thienyl or perfluoroalkyl, acyl ordialkylamino, with, in each case, 5 carbon atoms in the alkyl part,alkoxy with 1 to 18 carbon atoms or phenoxy and R is hydrogen, alkylwith 1 to 18 carbon atoms, aralkyl, aryl, cycloalkyl, alkoxy with 1 to18 carbon atoms, aryloxy, alkylmercapto with 1 to 18 carbon atoms,arylmercapto, halogen, trifluoromethyl, cyano, a primary amino group ora mono- or di-alkylamino group, the alkyl radicals of which each contain1 to 18 carbon atoms, or one of the groups ##STR27## in which alkylcontains 1 to 5 carbon atoms, M--Z--HN--, W--CO--, W--SO₂ --, W--CO--O--and W--O--CO--, in which M, W and Z have the indicated meanings.

In some cases compounds of the formula ##STR28## in which G, Z, M and Rhave the indicated meaning but at least one of the radicals M and Rcontains a benzene nucleus and these benzene nuclei are preferablybonded direct to the heterocyclic radical or to Z, prove to be valuableyellow couplers.

Materials, for colour photography, which contain, as yellow couplers,compounds of the formula ##STR29## in which G₁ is an open-chain radical,containing a methylene group, of a yellow coupler and R, M and Z havethe indicated meanings, or of the formula ##STR30## in which G₂ is abenzoylacetanilide or pivaloylacetanilide radical and R, M and Z havethe indicated meanings, are also particularly suitable.

Preferred representatives of the compounds of the formula (3) are thoseof the formulae ##STR31## in which E₁ is alkyl with 1 to 20 carbon atomsand E₂ is hydrogen or alkyl with 1 to 20 carbon atoms and R, M and Zhave the indicated meanings, and ##STR32## in which E₃ is chlorine andalkyl or alkoxy with 1 to 4 carbon atoms and R, M and Z have theindicated meanings. E₃ in formula (5) is preferably chlorine.

Materials, for colour photography, which contain, as yellow couplers,compounds of the formulae ##STR33## in which M₁ is alkyl with 1 to 13carbon atoms, optionally substituted by halogen, alkoxy with 1 to 5carbon atoms or optionally substituted phenoxy; alkoxy with 1 to 5carbon atoms; benzyl, cycloalkyl, phenyl, optionally substituted byalkyl or alkoxy with 1 to 5 carbon atoms, halogen, nitro or --NHCOC_(n)H_(2n+1), in which n is 1 to 5; pyridyl, phenylamino or dialkylaminowith in each case, 1 to 5 carbon atoms in the alkyl part, R₁ ishydrogen, alkyl with 1 to 12 carbon atoms, benzyl, phenyl, thienyl,cycloalkyl with 1 to 4 cycloalkyl rings, alkoxy with 1 to 5 carbonatoms, alkylmercapto with 1 to 4 carbon atoms, halogen, benzoylbenzoyloxyalkyl with 1 to 5 carbon atoms in the alkyl part, benzylamino,mono- or di-alkylamino with 1 to 5 carbon atoms in the alkyl part, SO₂NH₂, N,N-dialkylsulphonamide with, in each case, 1 to 5 carbon atoms inthe alkyl part, or --NHCOC_(n) H_(2n+1), in which n is 1 to 5, and Z is--CO-- or --SO₂ --, and ##STR34## in which M₂ is straight-chain orbranched alkyl with 1 to 7 carbon atons, --CH₂ Cl, --CCl₃, --CH₂ OC₂ H₅,##STR35## alkoxy with 1 or 2 carbon atoms, benzyl, phenyl, tolyl,t-butylphenyl, methoxyphenyl, dimethoxyphenyl, chlorophenyl,dichlorophenyl, nitrophenyl, acetylaminophenyl, pyridyl, anilino ordimethylamino, R₂ is hydrogen, alkyl with 1 to 12 carbon atoms, phenyl,benzyl, thienyl, cyclohexyl, norbornyl, 1-adamantyl, alkoxy with 1 to 3carbon atoms, alkylmercapto with 1 to 4 carbon atoms, chlorine, bromine,benzoyl, benzoyloxyalkyl with 1 to 3 carbon atoms in the alkyl part,benzylamino, mono- or di-alkylamino with 1 or 2 carbon atoms in thealkyl part, N,N-dialkylsulphonamide with 1 or 2 carbon atoms in thealkyl part or --NHCOC_(n).sbsb.1 H_(2n).sbsb.1₊₁, in which n₁ is 1 or 2,and Z is --CO-- or --SO₂ --, are also particularly preferred.

The radical R₂ in the compounds of the formula (7), in which Z is, inparticular, --CO--, is preferably hydrogen, alkyl with 1 to 12 carbonatoms, phenyl, benzyl, thienyl, cyclohexyl, 1-adamantyl, methoxy,ethoxy, propoxy, methylmercapto, propylmercapto, chlorine, bromine,benzoyl, benzoyloxymethyl, benzylamino, methylamino, diethylamino, --SO₂N(CH₃)₂ or --NHCOCH₃.

Finally, materials, for colour photography, which contain, as yellowcouplers, compounds of the formula ##STR36## in which M₃ is methyl,t-butyl, p-tolyl, p-chlorophenyl or p-acetylaminophenyl and R₃ ishydrogen, alkyl with 1 to 10 carbon atoms, cyclohexyl, 1-adamantyl,methoxy, i-propoxy, methylmercapto, chlorine, bromine, phenyl, benzyl orthienyl, are also particularly valuable.

The leaving groups of the formula ##STR37## in which M, R and Z have theindicated meanings, can be introduced into the yellow couplers usingknown starting materials.

Appropriately, 2-acylamino-1,3,4-thiadiazoles are reacted, in a mannerwhich is in itself known, with halogen compounds of the formulae Cl--Gor Br--G (in which the halogen atom replaces a hydrogen atom of theactive methylene group of the corresponding four-equivalent coupler) ininert organic solvents, such as acetonitrile, propionitrile ordimethylformamide, in the presence of an acid-binding agent, to give thecompounds, according to the invention, of the formulae (1) to (8). Theazeniate ion corresponding to the 2-acylamino-1,3,4-thiadiazole can alsobe synthesised independently and then reacted with the compounds Cl--Gor Br--G. This azeniate ion, which primarily is also formed from the2-acylamino-1,3,4-thiadiazole and the acid-binding agent, has thefollowing formula, to which a corresponding mesomeric canonical formulacan be assigned. ##STR38##

Depending on the relative electron density on the two nitrogen atomsparticipating in the mesomerism, which density in turn, of course,depends on the substituents R and --Z--M, the reaction with the reactantG--Cl or G--Br can now take place either on the ring nitrogen or on theexocyclic nitrogen. As a result, the corresponding isomeric compoundsare then formed. This behaviour has been described in the literature forother mesomeric educts and in the case of ambident anions (in thisconnection compare, for example, R. Gompper, Angew. Chem. 76, 412[1964]).

It has also been found that, in the category of compounds investigated,this isomerism (when it occurs at all) has no influence on the useproperties which are sought. Therefore, a detailed description of theisomeric forms possible in each case is dispensed with. However, it isobvious that each of the possible forms can be used for the desiredapplication.

The yellow couplers according to the invention represent a category ofcompounds which, in itself, is new. They are distinguished by highreactivity (high maximum density), minimal fogging, high fastness tolight, both of the couplers and of the dyestuffs formed, and excellentspectral properties of the dyestuffs formed.

According to the reaction equation ##STR39## the compounds of theformula (13) can be manufactured from the 2-amino-1,3,4-thiadiazoles ofthe formula (12) by known methods by reacting the aminothiadiazole ofthe formula (12) in the presence of bases, in an inert organic solvent,with an acid chloride or acid bromide, as is described, for example, byJ. Indian Chem. Soc. Vol. LII, May 1975, page 433-435 and in J. Chem.Soc. (C), 2700 (1967). The acid halides, in which Z denotes a --CO--group, are derived, for example, from the following carboxylic acids andcarboxylic acid derivatives: acetic acid, formic acid, propionic acid,butyric acid, isobutyric acid, 2-methylbutyric acid, valeric acid,isovaleric acid, caproic acid, caprylic acid, capric acid, dodecanoicacid, tetradecanoic acid, palmitic acid, stearic acid,cyclohexanecarboxylic acid, pivalic acid, chloroacetic acid,dichloroacetic acid, trichloroacetic acid, methoxyacetic acid,ethoxyacetic acid, phenylacetic acid, phenoxyacetic acid,2,4-di-t-pentylphenoxyacetic acid, 4-t-pentylphenoxyacetic acid,N,N-dimethylcarbamic acid, monomethyl carbonate, monomethoxyethylcarbonate, monoisopropyl carbonate, monoisobutyl carbonate, monophenylcarbonate, monobenzyl carbonate, mono-t-butyl carbonate, benzoic acid,o-toluic acid, m-toluic acid p-toluic acid, o-chlorobenzoic acid,m-chlorobenzoic acid, p-chlorobenzoic acid, m-methoxybenzoic acid,p-methoxybenzoic acid, p-bromobenzoic acid, m-dimethylaminobenzoic acid,m-cyanobenzoic acid, p-cyanobenzoic acid, p-methylsulphonylbenzoic acid,m-methylsulphonylbenzoic acid, m-trifluoromethylbenzoic acid,3,4-dimethylbenzoic acid, 2,4-dimethylbenzoic acid, 3,4-dimethoxybenzoicacid, 3,5-dimethoxybenzoic acid, 2,4-dimethoxybenzoic acid,p-t-butylbenzoic acid, 3,4-dichlorobenzoic acid, 2,4-dichlorobenzoicacid, pyridine-2-carboxylic acid, pyridine-3-carboxylic acid,pyridine-4-carboxylic acid, thiophene-2-carboxylic acid,furane-2-carboxylic acid, naphthalene-1-carboxylic acid,naphthalene-2-carboxylic acid, 4-methoxycarbonylbenzoic acid and4-ethoxycarbonylbenzoic acid.

The sulphonic acid halides, in which Z denotes a --SO₂ -- group, arederived, for example, from the following sulphonic acids:methanesulphonic acid, trifluoromethanesulphonic acid, benzenesulphonicacid, p-acetylaminobenzenesulphonic acid, o- or p-toluenesulphonic acid,xylenesulphonic acid, pyridine-3-sulphonic acid, naphthalene-1-sulphonicacid and naphthalene-2-sulphonic acid.

The aminothiadiazoles of the formula (12) are compounds which are knownfrom the literature. They can be manufactured by various methods, suchas, for example, are described in J. Indian Chem. Soc. Vol. LII, May1975, page 433-35, in U.S. Pat. No. 2,623,877, in J. Chem. Soc. (C),2702 [1967], in Acta Chimica Scandinavica 18, 174-184 [1964], in J. Het.Chem. Vol. 12, 581, 841 [1975], in J. Chem. Soc. (C) 2932 [1971], in J.Chem. Soc. (C) 2927 [1971], in Eur. J. Med. Chem. 10, page 121-24[1975], J. Chem. Soc. 1163 [1949], in British Patent Specification916,061, J. Prakt. Chemie 122, 289 [1929], J. Prakt. Chemie 122, 303[1929] and J. Chem. Soc. 1509 [1958]. The following atoms or groupingscan be mentioned as radicals R in formula (12): hydrogen, methyl, ethyl,propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, cyclohexyl, heptyl,undecyl, ethoxymethyl, hydroxymethyl, benzyl, methoxy, hydroxyl, ethoxy,isopropoxy, propoxy, butoxy, phenoxy, acetoxy, benzoyloxy, amino,acetylamino, methylamino, dimethylamino, phenylamino, chlorine, bromine,methylmercapto, ethylmercapto, propylmercapto, isopropylmercapto,phenylmercapto, methylsulphonyl, phenylsulphonyl, acetyl, benzoyl,methylsulphonylamino, phenyl, 4-methoxyphenyl, 3,5-dimethoxyphenyl,2-methoxyphenyl, 3-methoxyphenyl, 2 -chlorophenyl, 3,4-dichlorophenyl,4-chlorophenyl, 4-cyanophenyl, 4-nitrophenyl, 2-methylphenyl,4-methylphenyl, 3-methylphenyl, 4-methylsulphonylphenyl, 4-bromophenyl,3-dimethylaminophenyl, 1-naphthyl, 2-naphthyl, 2-pyridyl, 3-pyridyl,4-pyridyl and 2-thienyl.

Starting materials of the formulae Cl--G and Br--G which can be employedfor the synthesis of the yellow coupler according to the invention arethe α-halogeno-acylacetanilides, which are known to those skilled in theart, such as the α-halogenoacylacetanilides which are described, interalia, in German Offenlegungsschrift 2,114,577, French PatentSpecifications Nos. 991,453 and 869,169 and U.S. Pat. Nos. 2,728,658 and3,277,155.

Thus, for example, the following compounds can be used:

1.α-Acetyl-α,2-dichloro-5-[α-(2',4'-di-tert.-amylphenoxy)-acetylamino]-acetanilide.

2.α-Pivalyl-α-bromo-2-chloro-5-[α'-(4'-tert.-amylphenoxy)-n-tetradecanoylamino]-acetanilide.

3.α-(β'-Methoxy-α',α'-dimethyl-propionyl)-α-chloro-4-[N-(γ"-phenylpropyl)-N-(p-tolyl)-carbamoylmethoxy]-acetanilide.

4.α-(α'-Methoxyisobutyryl)-α-chloro-2-methoxy-5-[γ-(3"-n-pentadecylphenoxy)-butyramino]-acetanilide.

5.α-(α'-Phenoxyisobutyryl)-α,2-dichloro-5-(n-octadecylsuccinimido)-acetanilide.

6.1-[α-(α',α'-Dimethylbutyryl)-α-chloro-acetylamino]-2-phenoxybenzene-5-carboxylicacid (di-n-butoxy)-phosphonoethylamide [--CO--NH--CH₂ --CH₂ --(OP)(O--C₄H₉)₂ ].

7.α-(α',α'-dimethyl-octadecanoyl)-α-bromo-3,5-bis-methoxy-carbonyl-acetanilide.

8.α-(α'-Ethyl-α'-methyl-hexanoyl)-α-bromo-2-chloro-5-[γ"-(2",4"-di-tert.-amylphenoxy)-butyramino]-acetanilide.

9.α-(α',α',γ',γ'-tetramethyl-valeryl)-α,2-dichloro-5-(n-dodecyloxycarbonyl)-acetanilide.

10.α-(1'-Methyl-cyclohexanecarbonyl)-α-bromo-2-chloro-5-[α"-(2",4"-di-tert.-amylphenoxy)-butyramino]-acetanilide.

11.α-(7',7'-Dimethylnorbornane-1'-carbonyl)-α,2-dichloro-5-[.alpha."-(2",4"-di-tert.-amylphenoxy)-acetamino]-acetanilide.

12.α-Benzoyl-α-chloro-2-methoxy-5-[α'-(3'-n-dodecyloxyphenoxy)butyramino]-acetanilide.

13.1-[α-(4'-Methoxybenzoyl)-α-chloro]-acetylamino-2-chloro-5-[.beta.-(N-palmityl-N-n-butyl-amino)-propionylamino]-benzene.

14.α-Piperonyloyl-α,2-dichloro-5-(α'-phenoxy-n-tetradecanoylamino)-acetanilide.

15. (α'-n-Dodecyloxycarbonyl)-ethyl1-[α-(2'-chlorobenzoyl)-α-chloro]-acetylaminobenzene-4-carboxylate.

16. α-(4'-Chlorobenzoyl)-α-bromo-2-hexadecyloxy-acetanilide.

17.α-Piperonyloyl-α-chloro-3-[(N-methyl-N-n-octadecyl)sulphamoyl]-acetanilide.

18.α-{3'-[γ-(2",4"-Di-t-amylphenoxy)-butyramino]-benzoyl}-α-bromo-4-chloro-2,5-dimethoxy-acetanilide.

19.α-{3'-[α"-(3"-n-Pentadecylphenoxy)-butyramino]-benzoyl}-.alpha.,2-dichloro-acetanilide,and

20. α-(4'-n-Hexadecyloxy-benzoyl)-α-chloro-2-methoxy-acetanilide.

The colour couplers of the formulae (1) to (8) can be incorporated, in aknown manner, in photographic layers, for example silver halideemulsions containing gelatine or binders.

For example, they can be used with silver bromide, silver chloride orsilver iodide emulsions or with those emulsions which contain a mixtureof silver halides, such as silver bromide/iodide or silverchloride/bromide emulsions.

The emulsions can be chemically sensitised and they can also containcustomary organic stabilisers and anti-fogging agents as well ascustomary plasticisers, such as, for example, glycerol. The emulsionscan also be hardened using the hardeners customary for gelatine.Furthermore, the emulsions can contain customary coating auxiliaries.The emulsions can be applied to customary layer carriers forphotographic recording material. A mixture of several colloids canoptionally be used for dispersing the silver halides.

The customary developer baths can be employed for developing therecording material for colour photography. These baths as a rule containa developing agent of the p-phenylenediamine type, a developmentretarder, such as potassium bromide, an antioxidant, such as sodiumsulphite, and a base, for example, an alkali metal hydroxide or alkalimetal carbonate. The developer baths can also contain a customaryanti-fogging agent and complex-forming agents.

Corresponding application possibilities are described, for example, inU.S. Pat. Nos. 2,304,939, 2,304,940, 2,322,027, 2,284,879, 2,801,170,2,801,171, 2,749,360 and 2,825,382.

General instructions for the manufacture of compounds of the formula(13) (leaving groups) ##STR40##

1 mol of the aminothiadiazole (12) is suspended in 500 ml of pyridineand the suspension is cooled to 0° to 10°. 1 mol of the carboxylic acidchloride (or of the corresponding sulphonic acid chloride) is added,with continuous stirring and cooling. The solution is allowed to reactfor 1 hour at 0° to 10° C and is then further stirred for between 2 and6 hours at room temperature. After concentrating to half its volume, thereaction mixture is poured into 1 l of water which previously has beenacidified (pH value: 2) with 2 N sulphuric acid. A precipitate separatesout and this is filtered off, washed with water until neutral, dried andrecrystallised from ethanol.

If the corresponding isocyanate is used in place of the acid chloride, acompound of the formula (13) in which --Z--M is --CO--NHR is formed inan analogous manner.

Examples of compounds of the formula (13) are given in Table I whichfollows.

                                      Table 1                                     __________________________________________________________________________                                        Melting                                   No.                                                                              R           Z    M               point, ° C                         __________________________________________________________________________    101                                                                               ##STR41##  CO                                                                                  ##STR42##      223-225                                   102                                                                              CH.sub.3 O  CO                                                                                  ##STR43##      211-213                                   103                                                                              CH.sub.3 O  SO.sub.2                                                                            ##STR44##      166-167                                   104                                                                              H           CO   CH.sub.3        277-279                                   105                                                                              CH.sub.3    CO   CH.sub.3        >280                                      106                                                                              H           CO   C.sub.2 H.sub.5 234-235                                   107                                                                              CH.sub.3    CO                                                                                  ##STR45##      243-244                                   108                                                                              CH.sub.3    CO                                                                                  ##STR46##      238-239                                   109                                                                              CH.sub.3    CO   (CH.sub.2).sub.12 CH.sub.3                                                                    196-199                                   110                                                                              CH.sub.3    CO                                                                                  ##STR47##      >270                                      111                                                                              CH.sub.3    CO                                                                                  ##STR48##      242-244                                   112                                                                              CH.sub.3S   CO   CH.sub.3        203-204                                   113                                                                               ##STR49##  CO   CH.sub.3        243-245                                   114                                                                              CH.sub.3    CO                                                                                  ##STR50##      248-249                                   115                                                                              CH.sub.3    CO   CCl.sub.3       207-209                                   116                                                                               ##STR51##  CO                                                                                  ##STR52##      263-264                                   117                                                                               ##STR53##  CO                                                                                  ##STR54##      201-203                                   118                                                                               ##STR55##  CO                                                                                  ##STR56##      160-162                                   119                                                                               ##STR57##  CO                                                                                  ##STR58##      272-273                                   120                                                                               ##STR59##  CO                                                                                  ##STR60##      212-213                                   121                                                                               ##STR61##  CO                                                                                  ##STR62##      280-281                                   122                                                                              Cl          CO                                                                                  ##STR63##      222-225                                   123                                                                               ##STR64##  CO   C(CH.sub.3).sub.3                                                                             193-195                                   124                                                                               ##STR65##  CO                                                                                  ##STR66##      196-198                                   125                                                                               ##STR67##  CO   CH.sub.2 Cl     222-223                                   126                                                                               ##STR68##  CO                                                                                  ##STR69##      208-209                                   127                                                                              CH.sub.3 S  CO                                                                                  ##STR70##      199-201                                   128                                                                               ##STR71##  CO                                                                                  ##STR72##      225-230                                   129                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                CO                                                                                  ##STR73##      151-156                                   130                                                                              H.sub.3 C(H.sub.2 C).sub.6                                                                 CO                                                                                 ##STR74##      108-113                                   131                                                                              (H.sub.3 C).sub.2HC                                                                       CO                                                                                  ##STR75##      154-158                                   132                                                                              H.sub.3 C(H.sub.2 C).sub.10                                                               CO                                                                                  ##STR76##      124-127                                   133                                                                               ##STR77##  CO                                                                                  ##STR78##      170-174                                   134                                                                              1-Adamantyl CO                                                                                  ##STR79##      296-300                                   135                                                                              (H.sub.3 C).sub.3 C                                                                       CO                                                                                  ##STR80##      224-230                                   136                                                                               ##STR81##  CO   (CH.sub.2).sub.6CH.sub.3                                                                      132-135                                   137                                                                              H.sub.3 C(H.sub.2 C).sub.6                                                                CO   C(CH.sub.3).sub.3                                                                             56-59                                     138                                                                              (H.sub.3 C).sub.3 C                                                                       CO   C(CH.sub.3).sub.3                                                                             183-186,5                                 139                                                                              H.sub.3 C(H.sub.2 C).sub.10                                                               CO   C(CH.sub.3).sub.3                                                                             64-68                                     140                                                                               ##STR82##  CO   C(CH.sub.3).sub.3                                                                             157-160                                   141                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                CO   C(CH.sub.3).sub.3                                                                             100-105                                   142                                                                               ##STR83##  CO   (CH.sub.2).sub.3 CH.sub.3                                                                     199-200                                   143                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                CO   (CH.sub.2).sub.3 CH.sub.3                                                                     153-156                                   144                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                CO   CCl.sub.3       wax-like                                  145                                                                              (H.sub.3 C).sub.2HCH.sub.2 C                                                              CO   CCl.sub.3       wax-like                                  146                                                                               ##STR84##  CO   N(CH.sub.3).sub.2                                                                             133-141                                   147                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                CO                                                                                  ##STR85##      199-200                                   148                                                                              (H.sub.3 C).sub.2HC                                                                       CO                                                                                  ##STR86##      143-150                                   149                                                                              (H.sub.3 C).sub.3 C                                                                        CO                                                                                 ##STR87##      104-116                                   150                                                                               ##STR88##  CO                                                                                  ##STR89##      233-236                                   151                                                                               ##STR90##  CO   C(CH.sub.3).sub.3                                                                             184-186                                   152                                                                               ##STR91##  CO   OCH.sub.2CH.sub.3                                                                             188-190                                   153                                                                               ##STR92##  CO   OCH.sub.2CH.sub.3                                                                             117-119                                   154                                                                              CH.sub.3S   CO   OCH.sub.2CH.sub.3                                                                             160-161                                   155                                                                               ##STR93##  CO   C(CH.sub.3).sub.3                                                                             103-105                                   156                                                                              CH.sub.3CH.sub.2S                                                                         CO                                                                                  ##STR94##      129-132                                   157                                                                               ##STR95##  CO                                                                                  ##STR96##      145-147                                   158                                                                               ##STR97##  CO   CH.sub.3        253-255                                   159                                                                               ##STR98##  CO                                                                                  ##STR99##      187-189                                   160                                                                              CH.sub.3 O  CO   C(CH.sub.3).sub.3                                                                             163-165                                   161                                                                              CH.sub.3 S  CO   C(CH.sub.3).sub.3                                                                             161-163                                   162                                                                              CH.sub.3 S  CO   CH.sub.2 OCH.sub.2 CH.sub.3                                                                   117-118                                   163                                                                               ##STR100## CO                                                                                  ##STR101##     >250                                      164                                                                               ##STR102## CO                                                                                  ##STR103##     236-240                                   165                                                                               ##STR104## CO   OCH.sub.3       225-227 decomposition                     166                                                                               ##STR105## CO                                                                                  ##STR106##     207-210                                   167                                                                              H           CO   OCH.sub.3       223                                                                           decomposition                             168                                                                               ##STR107## CO                                                                                  ##STR108##     128-132                                   169                                                                               ##STR109## CO                                                                                  ##STR110##     221-222                                   170                                                                              H           CO                                                                                  ##STR111##     198-201                                   171                                                                               ##STR112## SO.sub.2                                                                            ##STR113##     151-154                                   172                                                                               ##STR114## SO.sub.2                                                                            ##STR115##     120-124                                   173                                                                               ##STR116## SO.sub.2                                                                            ##STR117##     186-190                                   174                                                                              H.sub.3 C(H.sub.2 C).sub.10                                                               SO.sub.2                                                                            ##STR118##     73-76                                     175                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                SO.sub.2                                                                            ##STR119##     123-126                                   176                                                                              1-Adamantyl-                                                                              SO.sub.2                                                                            ##STR120##     228-236                                   177                                                                              (H.sub.3 C).sub.2HC                                                                       SO.sub.2                                                                            ##STR121##     123-125                                   178                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                SO.sub.2                                                                           CH.sub.3        90-93                                     179                                                                               ##STR122## SO.sub.2                                                                            ##STR123##     199-202                                   180                                                                               ##STR124## SO.sub.2                                                                            ##STR125##     152-155                                   181                                                                               ##STR126## SO.sub.2                                                                            ##STR127##     215-217                                   182                                                                              CH.sub.3O   SO.sub.2                                                                            ##STR128##     170-172                                   183                                                                               ##STR129## SO.sub.2                                                                            ##STR130##     210-212                                   184                                                                              CH.sub.3 S  SO.sub.2                                                                            ##STR131##     172-174                                   185                                                                              Br          SO.sub.2                                                                            ##STR132##     149-153                                   186                                                                              H           SO.sub.2                                                                            ##STR133##     170-176                                   __________________________________________________________________________

EXAMPLE 1α-[3-(2-Benzoylimino-5-phenyl-1,3,4-thiadiazolinyl]-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)-butyramino]-acetanilide.

A mixture of 351 mg (1.1 mmols) of the potassium salt of2-benzoylamino-5-phenyl-1,3,4-thiadiazole and 650 mg (1 mmol) ofα-pivalyl-α-bromo-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)-butyramino]-acetanilideis stirred in 15 ml of absolute acetonitrile for 3 hours at roomtemperature. The yellow suspension is poured into 250 ml of water, thepH of which has previously been adjusted to 2.5 with 2 N hydrochloricacid. The white precipitate is filtered off, washed with a little waterand recrystallised from ethanol. This gives 480 mg of the acetanilide ofthe formula ##STR134## with a melting point of 127° to 131° C.

D_(max) : 1.40 (compare Example 7).

EXAMPLE 2

In the manner described in Example 1, the potassium salt of2-benzoylamino-5methoxy-1,3,4-thiadiazole is reacted with theacetanilide of the indicated composition. The product of the formula##STR135## which is thus obtained, melts at 149° to 150° C.

D_(max) : 1.66.

EXAMPLE 3

In the manner described in Example 1, the potassium salt of2-p-toluenesulphonylamino-5-methoxy-1,3,4-thiadiazole is reacted withthe same acetanilide. This gives a product which melts at 150° to 152° Cwith decomposition and corresponds to the formula ##STR136##

D_(max) : 1.66.

The other compounds of the formula ##STR137## indicated in Table IIwhich follows can also be manufactured in an analogous manner.

At the same time, the maximum density D_(max) at the absorption maximum(442-444 nm) is given for the yellow dyestuffs obtained from the yellowcouplers after exposure and photographic development (according toExample 7).

                                      Table II                                    __________________________________________________________________________                                               Melting                            No.                                                                              R               Z    M                  point, ° C                                                                  D.sub.max                     __________________________________________________________________________    204                                                                              H               CO   CH.sub.3            94 - 103                                                                          1.38                          205                                                                              H.sub.3 C       CO   CH.sub.3           92 - 97                                                                            1.45                          206                                                                              H               CO   C.sub.2 H.sub.5    92 - 98                                                                            1.21                          207                                                                              H.sub.3 C       CO                                                                                  ##STR138##        176 - 180                                                                          1.52                          208                                                                              H.sub.3 C       CO                                                                                  ##STR139##        166 - 167                                                                          1.59                          209                                                                              H.sub.3 C       CO   (CH.sub.2).sub.12CH.sub.3                                                                        141 - 142                                                                          1.16                          210                                                                              H.sub.3 C       CO                                                                                  ##STR140##        151 - 153                                                                          1.15                          211                                                                              H.sub.3 C       CO                                                                                  ##STR141##        132 - 134                                                                          1.35                          212                                                                              H.sub.3 CS      CO   CH.sub.3           110 - 112                                                                          1.45                          213                                                                               ##STR142##     CO   CH.sub.3            98 - 102                                                                          1.38                          214                                                                              H.sub.3 C       CO                                                                                  ##STR143##        140 - 143                                                                          1.30                          215                                                                              H.sub.3 C       CO   CCl.sub.3          183 - 186                                                                          1.43                          216                                                                               ##STR144##     CO                                                                                  ##STR145##        183 - 188                                                                          1.36                          217                                                                               ##STR146##     CO                                                                                  ##STR147##        101 - 114                                                                          1.27                          218                                                                               ##STR148##     CO                                                                                  ##STR149##        110 - 125                                                                          1.39                          219                                                                               ##STR150##     CO                                                                                  ##STR151##        178 - 180                                                                          1.37                          220                                                                               ##STR152##     CO                                                                                  ##STR153##        174 - 177                                                                          1,40                          221                                                                               ##STR154##     CO                                                                                  ##STR155##        160 - 161                                                                          1.21                          222                                                                              Cl              CO                                                                                  ##STR156##        164 - 165                                                                          1.45                          223                                                                               ##STR157##     CO   C(CH.sub.3).sub.3  95 - 99                                                                            1,51                          224                                                                               ##STR158##     CO                                                                                  ##STR159##        100 - 107                                                                          1.44                          225                                                                               ##STR160##     CO   CH.sub.2 Cl        149 - 150                                                                          1.39                          226                                                                               ##STR161##     CO                                                                                  ##STR162##        139 - 141                                                                          1.21                          227                                                                              H.sub.3 CS      CO                                                                                  ##STR163##         98 - 106                                                                          1.39                          228                                                                               ##STR164##     CO                                                                                  ##STR165##        118 - 121                                                                          1.20                          229                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                    CO                                                                                  ##STR166##        151 - 153                                                                          1.39                          230                                                                              H.sub.3 C(H.sub.2 C).sub.6                                                                    CO                                                                                  ##STR167##        153 - 155                                                                          1.12                          231                                                                              (H.sub.3 C).sub.2HC                                                                           CO                                                                                  ##STR168##        148 - 150                                                                          1.51                          232                                                                              H.sub.3 C(H.sub.2 C).sub.10                                                                   CO                                                                                  ##STR169##        163 - 165                                                                          1.43                          233                                                                               ##STR170##     CO                                                                                  ##STR171##        149 - 153                                                                          1.26                          234                                                                              1-Adamantyl-    CO                                                                                  ##STR172##        157 - 159                                                                          1.41                          235                                                                              (H.sub.3 C).sub.3 C                                                                           CO                                                                                  ##STR173##        121 - 124                                                                          1.31                          236                                                                               ##STR174##     CO   (CH.sub.2).sub.6CH.sub.3                                                                         83 - 85                                                                            1.32                          237                                                                              H.sub.3 C(H.sub.2 C).sub.6                                                                    CO   C(CH.sub.3).sub.3  130 - 132                                                                          1.37                          238                                                                              (H.sub.3 C).sub.3 C                                                                           CO   C(CH.sub.3).sub.3  157 - 159                                                                          1.41                          239                                                                              H.sub.3 C(H.sub.2 C).sub.10                                                                   CO   C(CH.sub.3).sub.3  152 - 154                                                                          1.33                          240                                                                               ##STR175##     CO   C(CH.sub.3).sub.3  98 - 103                                                                           1.36                          241                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                    CO   C(CH.sub.3).sub.3  125,5 - 128                                                                        1.32                          242                                                                               ##STR176##     CO   (CH.sub.2).sub.3 CH.sub.3                                                                        189 - 191                                                                          1.48                          243                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                    CO   (CH.sub.2).sub.3 CH.sub.3                                                                        183 - 185                                                                          1.36                          244                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                    CO   CCl.sub.3          151 - 153                                                                          1.38                          245                                                                              (H.sub.3 C).sub.2HCH.sub.2 C                                                                  CO   CCl.sub.3          193 - 196                                                                          1.47                          246                                                                               ##STR177##     CO   N(CH.sub.3).sub.2  118 - 121                                                                          1.30                          247                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                    CO                                                                                  ##STR178##        134 - 136                                                                          1.26                          248                                                                              (H.sub.3 C).sub.2HC                                                                           CO                                                                                  ##STR179##        174 - 176                                                                          1.29                          249                                                                              (H.sub.3 C).sub.3 C                                                                           CO                                                                                  ##STR180##        159 - 162                                                                          1.48                          250                                                                               ##STR181##     CO                                                                                  ##STR182##        126 - 127                                                                          1.24                          251                                                                               ##STR183##     CO   C(CH.sub.3).sub.3  185 - 186                                                                          1.52                          252                                                                               ##STR184##     CO   OCH.sub.2CH.sub.3  176 - 179                                                                          1.46                          253                                                                               ##STR185##     CO   OCH.sub.2 CH.sub.3 82 - 83                                                                            1.50                          254                                                                              CH.sub.3S       CO   OCH.sub.2 CH.sub.3 154 - 155                                                                          1.39                          255                                                                               ##STR186##     CO   C(CH.sub.3).sub.3  75 - 85                                                                            1.35                          256                                                                              CH.sub.3 CH.sub.2S                                                                            CO                                                                                  ##STR187##        93 - 97                                                                            1.39                          257                                                                               ##STR188##     CO                                                                                  ##STR189##        140 - 141                                                                          1.56                          258                                                                               ##STR190##     CO   CH.sub.3           160 - 163                                                                          1.36                          259                                                                               ##STR191##     CO                                                                                  ##STR192##        137 - 140                                                                          1.28                          260                                                                              CH.sub.3 O      CO   C(CH.sub.3).sub.3  116 - 118                                                                          1.32                          261                                                                              CH.sub.3 S      CO   C(CH.sub.3).sub.3  139 - 141                                                                          1.59                          262                                                                              CH.sub.3 S      CO   CH.sub.2 OCH.sub.2 CH.sub.3                                                                      102 - 106                                                                          1.49                          263                                                                               ##STR193##     CO                                                                                  ##STR194##        178 - 182                                                                          1.33                          264                                                                               ##STR195##     CO                                                                                  ##STR196##        115 - 118                                                                          1.41                          265                                                                               ##STR197##     CO   OCH.sub.3          162 - 165                                                                          1.43                          266                                                                               ##STR198##     CO                                                                                  ##STR199##        90 - 93                                                                            1.52                          267                                                                              H               CO   OCH.sub.3           99 - 102                                                                          1.51                          268                                                                               ##STR200##     CO                                                                                  ##STR201##        136 - 139                                                                          1.38                          269                                                                               ##STR202##     CO                                                                                  ##STR203##        114 - 120                                                                          1.17                          270                                                                              H               CO                                                                                  ##STR204##        125 - 128                                                                          1.49                          271                                                                               ##STR205##     SO.sub.2                                                                            ##STR206##        135 - 139                                                                          1.22                          272                                                                               ##STR207##     SO.sub.2                                                                            ##STR208##        183 - 185                                                                          1.30                          273                                                                               ##STR209##     SO.sub.2                                                                            ##STR210##        190 - 192                                                                          1.34                          274                                                                              H.sub.3 C(H.sub.2 C).sub.10                                                                   SO.sub.2                                                                            ##STR211##        121 - 123                                                                          1.33                          275                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                    SO.sub.2                                                                            ##STR212##        172 - 174                                                                          1.21                          276                                                                              1-Adamantyl     SO.sub.2                                                                            ##STR213##        217 - 220                                                                          1.34                          277                                                                              (H.sub.3 C).sub.2CH                                                                           SO.sub.2                                                                            ##STR214##        168 - 169                                                                          1.45                          278                                                                              H.sub.3 C(H.sub.2 C).sub.3                                                                    SO.sub.2                                                                           CH.sub.3           212 - 213                                                                          1.31                          279                                                                               ##STR215##     SO.sub.2                                                                            ##STR216##        197 - 198                                                                          1.49                          280                                                                               ##STR217##     SO.sub.2                                                                            ##STR218##        181 - 184                                                                          1.42                          281                                                                               ##STR219##     SO.sub.2                                                                            ##STR220##        194 - 196                                                                          1.30                          282                                                                              CH.sub.3O       SO.sub.2                                                                            ##STR221##        179 - 181                                                                          1.58                          283                                                                               ##STR222##     SO.sub.2                                                                            ##STR223##        192 - 193                                                                          1.32                          284                                                                              CH.sub.3 S      SO.sub.2                                                                            ##STR224##        144 - 147                                                                          1.45                          285                                                                              Br              SO.sub.2                                                                            ##STR225##        73 - 76                                                                            1.18                          286                                                                              H               SO.sub.2                                                                            ##STR226##        128 - 130                                                                          1.56                          __________________________________________________________________________

EXAMPLE 4

2.1 g ofα-chloro-α-{3-[γ-(2,4-di-tert.-pentyl-phenoxy)butyramino]-benzoyl}-4-chloro-2,5-dimethoxy-acetanilide,1.3 g of 2-isopropyl-5-p-toluenesulphonimido-4H-1,3,4-thiadiazoline and300 mg of pulverulent potassium hydroxide was stirred in 30 ml ofacetonitrile for 5 hours at room temperature. The residue obtained afterdistilling off the solvent is chromatographed on 60 g of silica gel andthe residue from the pure fractions is recrystallised from 1:3:8benzene/ether/hexane.

This gives the coupler of the formula ##STR227## in the form of a whitepowder with a melting point of 110°-112° C.

D_(max) : 1.85

The further compounds of the formulae ##STR228## Melting point: 55° C

D_(max) : 1.59 ##STR229## Melting point: 85°-90° C

D_(max) : 1.26 and ##STR230## Melting point: 65° to 70° C

D_(max) : 1.64 are obtained in an analogous manner.

EXAMPLE 5

9.6 g of α-chloro-α-pivalyl-2-chloro-5-n-dodecyloxycarbonyl-acetanilideand 2.88 g of the potassium salt of2-isopropyl-5-p-toluene-sulphonimido-1,3,4-thiadiazoline are stirred in80 ml of ethyl acetate for 3 hours at room temperature. The resultingcrude product is recrystallised three times from ether/hexane.

This gives the coupler of the formula ##STR231## with a melting point of48°-52° C.

D_(max) : 1.48

The couplers of the following formulae: ##STR232## Melting point:70°-73° C

D_(max) : 1.28 ##STR233## Melting point: 49°-52° C

D_(max) : 1.17 ##STR234## Melting point: 79°-81° C

D_(max) : 1.20 ##STR235## Melting point: 61°-65° C

D_(max) : 1.19 ##STR236## Melting point: 79°-81° C

D_(max) : 1.20 and ##STR237## Melting point: 61°-65° C

D_(max) : 1.19 are obtained in an analogous manner.

EXAMPLE 6

6.5 g ofα-bromo-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amyl-phenoxy)-butyramino]-acetanilide,2.1 g of bis-[N,N'-5-t-butyl-1,3,4-thiadiazolyl-2-]-adipic acid diamideand 2.0 g of potassium carbonate are stirred in 70 ml oftridimethylaminophosphine oxide for 3 days at room temperature. Theyellow solution is poured into 200 ml of water and extracted withchloroform and the chloroform phase is washed several times with 2 Nhydrochloric acid and evaporated. The oil formed is chromatographed onsilica gel using 1:4 ethyl acetate/petroleum ether. This gives 1.2 g ofthe acetanilide of the formula ##STR238## λ_(max) = 442 nm, D_(max) =1.45 (compare Example 7 for the determination of D_(max)).

In addition, 1.5 g of the acetanilide of the formula ##STR239## areobtained.

Melting point: 154°-156° C.

EXAMPLE 7

0.1 mmol of the yellow coupler of the formula (201), the preparation ofwhich is described in Example 1, is dissolved in 2.0 ml of tricresylphosphate/methylene chloride (1:9). The methylene chloride is evaporatedoff, 2.0 ml of an 8% strength aqueous solution of sodiumisopropylnaphthalenesulphonate, 6.6 ml of 6% strength gelatine solutionand 1.2 ml of water are added, the pH of the mixture is adjusted to 6.5and the mixture is emulsified for 5 minutes with the aid of anultrasonic device with an output of 100 watts.

2.5 ml of the coupler emulsion, freshly exposed to ultrasonic waves, 1.6ml of silver bromide emulsion which has a pH of 6.5 and contains 1.4% ofsilver and 6.0% of gelatine, 1.0 ml of a 1% strength aqueous solution ofthe hardener of the formula ##STR240## and 5.0 ml of water are mixedtogether and coated, at 40° C, onto a subbed 13 cm × 18 cm glass plate.

After the mixture has solidified at 10° C, the plate is dried in acirculating air drying cabinet at room temperature.

A strip cut to 4.0 cm × 6.5 cm is exposed, at 500 lux, under a stepwedge for 2 seconds and then treated at 24° C in the following way:

    ______________________________________                                                              Minutes                                                 ______________________________________                                        1. Colour development  5                                                      2. Washing             5                                                      3. First fixing        2                                                      4. Washing             2                                                      5. Silver bleaching    4                                                      6. Washing             2                                                      7. Second fixing       4                                                      8. Washing             10                                                     9. Drying              10                                                     ______________________________________                                    

Colour developers of the following compositions can be used forprocessing:

    ______________________________________                                        (a) 4-Amino-3-methyl-N-ethyl-N-[β-(methyl-                                sulphonamido)-ethyl]-aniline . 11/2 H.sub.2 SO.sub.4  .                                                 10 mmols/l                                         Anhydrous sodium sulphite                                                                               2.0 g/l                                             Potassium bromide         0.5 g/l                                             Potassium carbonate      40.0 g/l                                             Benzyl alcohol           10.0 ml/l                                            (pH: 10.7)                                                                    or                                                                            (b) 4-Amino-3-methyl-N-ethyl-N-[β-(methyl-                                sulphonamido)-ethyl]-aniline . 11/2 H.sub.2 SO.sub.4 .                                                  10 mmols/l                                         Anhydrous sodium sulphite                                                                               2.0 g/l                                             Potassium bromide         0.5 g/l                                             Potassium carbonate      40.0 g/l                                             (pH: 10.7)                                                                    ______________________________________                                    

Conventional baths are used for fixing and silver bleaching.

A clear, sharp yellow wedge which has an absorption maximum at 444 nmand a maximum density D_(max) of 1.40, is obtained in the mannerdescribed above.

EXAMPLE 8 (Comparison example)

The procedure according to the instructions of Example 7 is followed,using the known colour couplers which follow. The yellow dyestuffsformed in general display a lower colour density at the absorptionmaximum than the yellow dyestuffs which are formed from the yellowcouplers according to the invention.

(a) German Offenlegungsschrift No. 2,057,941, coupler (1). ##STR241##

(b) German Offenlegungsschrift No. 2,261,361, coupler (29) ##STR242##

(c) German Offenlegungsschrift No. 2,431,480, coupler (43) ##STR243##

(d) German Offenlegungsschrift No. 2,528,638, coupler (1) ##STR244## and

(e) German Offenlegungsschrift No. 2,528,638 coupler (17) ##STR245##

What is claimed is:
 1. Colour photographic material which comprises atleast one silver halide emulsion layer containing, as the yellowcoupler, a compound of the formulain which G₂ is a benzoylacetanilide orpivaloylacetanilide radical which is bonded to the heterocyclic ring bymeans of the active methylene group, Z is --CO-- or --SO₂ --, M is alkylwith 1 to 18 carbon atoms, optionally substituted by halogen, hydroxyl,nitro, cyano, alkoxy, aryloxy or amino; aralkyl, cycloalkyl with 1 to 4cycloalkyl rings, phenyl, optionally substituted by lower alkyl or loweralkoxy, halogen, acylamino, sulphonic acid groups, sulphonic acid amidegroups, carboxylic acid groups, carboxylic acid amide groups, carboxylicacid ester groups, hydroxyl, nitro, cyano, amino, mercapto,alkylmercapto or --SO₂ W or --COW, in which W is alkyl with 1 to 18carbon atoms, optionally substituted by halogen, nitro, cyano, amino oralkoxy with 1 to 18 carbon atoms; cycloalkyl, aryl, pyridyl, pyrimidyl,furyl or thienyl; M is also pyridyl, furyl, thienyl or perfluoroalkyl,acyl or dialkylamino with, in each case, up to 5 carbon atoms in thealkyl part; alkoxy with 1 to 18 carbon atoms or phenoxy; 1) M is furtherhydrogen, when Z is --CO--, and R is hydrogen or alkyl with 1 to 18carbon atoms, aralkyl, aryl, pyridyl, pyrimidyl, furyl, thienyl,cycloalkyl, alkoxy with 1 to 18 carbon atoms, aryloxy, alkylmercaptowith 1 to 18 carbon atoms, arylmercapto, halogen, acyl, acyloxyalkyl,trifluoromethyl, cyano, a primary amino group, a mono- or di-alkylaminogroup, in which the alkyl radicals each contain 1 to 18 carbon atoms, orone of the groups M--Z--HN--, W--CO--, ##STR246## W--SO₂ --, --SO₂ NH₂,##STR247## W--CO--O-- or W--O--CO--, in which E is alkyl with 1 to 5carbon atoms, E' is hydrogen or alkyl with 1 to 5 carbon atoms and M, Wand Z have the indicated meanings.
 2. Colour photographic materialaccording to claim 1, wherein the yellow coupler corresponds to theformula ##STR248## in which G₂ has the meaning indicated in claim 1, Zis --CO-- or --SO₂ --, M is alkyl with 1 to 18 carbon atoms, optionallysubstituted by halogen, nitro, cyano, alkoxy or amino, aralkyl,cycloalkyl, phenyl, optionally substituted by alkyl, alkoxy, halogen,acylamino, sulphonic acid groups, sulphonic acid amide groups,carboxylic acid groups, carboxylic acid groups, carboxylic acid amidegroups, carboxylic acid ester groups, hydroxyl, nitro, cyano, amino,mercapto alkylmercapto or --SO₂ --W or --CO--W, in which W is alkyl with1 to 18 carbon atoms, optionally substituted by halogen, nitro, amino oralkoxy with 1 to 18 carbon atoms; or cycloalkyl, aryl, pyridyl,pyrimidyl, furyl or thienyl; M is also pyridyl, furyl, thienyl orperfluoroalkyl, acyl or dialkylamino with, in each case, up to 5 carbonatoms in the alkyl part, alkoxy with 1 to 18 carbon atoms or phenoxy andR is hydrogen, alkyl with 1 to 18 carbon atoms, aralkyl, aryl,cycloalkyl, alkoxy with 1 to 18 carbon atoms, aryloxy, alkylmercaptowith 1 to 18 carbon atoms, arylmercapto, halogen, trifluoromethyl,cyano, a primary amino group or a mono- or di-alkylamino group, thealkyl radicals of which each contain 1 to 18 carbon atoms, or one of thegroups ##STR249## in which alkyl contains 1 to 5 carbon atoms,M--Z--HN--, W--CO--, W--SO₂ --, W--CO--O-- or W--O--CO--, in which M, Wand Z have the indicated meanings.
 3. Colour photographic materialaccording to claim 2, wherein the yellow coupler corresponds to theformula ##STR250## in which G₂, Z, M and R have the meanings indicatedin claim 2, but at least one of the radicals M and R contains a benzenenucleus and this benzene nucleus is preferably bonded direct to theheterocyclic ring or to Z.
 4. Colour photographic material according toclaim 1, wherein the yellow coupler corresponds to the formula##STR251## in which E₁ is alkyl with 1 to 20 carbon atoms and E₂ ishydrogen or alkyl with 1 to 20 carbon atoms and R, M and Z have themeanings indicated in claim
 1. 5. Colour photographic material accordingto claim 1, wherein the yellow coupler corresponds to the formula##STR252## in which E₃ is chlorine or alkyl or alkoxy with 1 to 4 carbonatoms and R, M and Z have the meanings indicated in claim
 1. 6. Colourphotographic material according to claim 1, wherein E₃ is chlorine. 7.Colour photographic material according to claim 6, wherein the yellowcoupler corresponds to the formula ##STR253## in which M₁ is alkyl with1 to 13 carbon atoms, optionally substituted by halogen, alkoxy with 1to 5 carbon atoms or optionally substituted phenoxy; alkoxy with 1 to 5carbon atoms; benzyl, cycloalkyl, phenyl, optionally substituted byalkyl or alkoxy with 1 to 5 carbon atoms, halogen, nitro or --NHCOC_(n)H_(2n+1), in which n is 1 to 5; pyridyl, phenylamino or dialkylaminowith, in each case, 1 to 5 carbon atoms in the alkyl part, R₁ ishydrogen, alkyl with 1 to 12 carbon atoms, benzyl, phenyl, thienyl,cycloalkyl with 1 to 4 cycloalkyl rings, alkoxy with 1 to 5 carbonatoms, alkylmercapto with 1 to 4 carbon atoms, halogen, benzoyl,benzoyloxyalkyl with 1 to 5 carbon atoms in the alkyl part,benzoylamino, mono- or di-alkylaminowith 1 to 5 carbon atoms in thealkyl part, SO₂ NH.sub. 2, N,N-dialkylsulphonamide with, in each case, 1to 5 carbon atoms in the alkyl part, or --NHCOC_(n) H_(2n+1), in which nis 1 to 5, and Z is --CO-- or --SO₂ --.
 8. Colour photographic materialaccording to claim 7, wherein the yellow coupler corresponds to theformula ##STR254## in which M₂ is straight-chain or branched alkyl with1 to 7 carbon atoms, --CH₂ Cl, --CCl₃, --CH₂ OC₂ H₅ ##STR255## alkoxywith 1 or 2 carbon atoms, benzyl, phenyl, tolyl, t-butylphenyl,methoxyphenyl, dimethoxyphenyl, chlorophenyl, dichlorophenyl,nitrophenyl, acetylaminophenyl, pyridyl, anilino or dimethylamino, R₂ ishydrogen, alkyl with 1 to 12 carbon atoms, phenyl, benzyl, thienyl,cyclohexyl, norbornyl, 1-adamantyl, alkoxy with 1 to 3 carbon atoms,alkylmercapto with 1 to 4 carbon atoms, chlorine, bromine, benzoyl,benzoyloxyalkyl with 1 to 3 carbon atoms in the alkyl part, benzylamino,mono- or di-alkylamino with 1 or 2 carbon atoms in the alkyl part,N,N-dialkylsulphonamide with 1 or 2 carbon atoms in the alkyl part or--NHCOC_(n).sbsb.1 H_(2n).sbsb.1₊₁, in which n₁ is 1 or 2, and Z is--CO-- or --SO₂ --.
 9. Colour photographic material according to claim8, wherein Z is --CO-- and R₂ is hydrogen, alkyl with 1 to 12 carbonatoms, phenyl, benzyl, thienyl, cyclohexyl, 1-adamantyl, methoxy,ethoxy, propoxy, methylmercapto, propylmercapto, chlorine, bromine,benzoyl, benzoyloxymethyl, benzylamino, methylamino, diethylamino, --SO₂N(CH₃)₂ or --NHCOCH₃ and M₂ has the meaning indicated in claim
 8. 10.Colour photographic material according to claim 8, wherein the yellowcoupler corresponds to the formula ##STR256## in which M₃ is methyl,t-butyl, p-tolyl, p-chlorophenyl or p-acetylaminophenyl and R₃ ishydrogen, alkyl with 1 to 10 carbon atoms, cyclohexyl, 1-adamantyl,methoxy, i-propoxy, methylmercapto, chlorine, bromine, phenyl, benzyl orthienyl.
 11. Process for the production of a yellow image, whereinmaterial for colour photography which contains on a support at least onelayer of silver halide emulsion containing as the yellow coupler atleast one compound according to claim 1, is exposed and the exposedmaterial is treated with an aqueous alkaline solution which contains anaromatic amine as the developer.